CHEM ENG 3029_7055

Materials Science and Engineering

 Lecture 6

Introduction to Corrosion and its Mechanisms

 Lecture Structure
Lecture 6 (Introduction to Corrosion and its Mechanisms) is divided into the following sections:
• L6.1 – Introduction to Corrosion
– Overview and Context
– Definition of Corrosion
– Importance of Corrosion in Engineering
– Cost of Corrosion
– Safety of Corrosion
• L6.2 – Introduction to Thermodynamics and Electrochemistry of Corrosion
– Thermodynamics of Corrosion
– Chemical and Free Energy
– Electrochemistry of Corrosion
– Predicting Corrosion: Standard EMF Series
• – Introduction to Types of Corrosion and Mechanisms
L6.3 – Formalisation of Corrosion
– Predicting and Monitoring Corrosion
– Formalisation Approach
– Thermodynamic Formalisation
– Electrochemical Potentials
– Electrochemical Double Layer
– Standard Hydrogen Electrode (SHE)
– Establishment of Electrochemical Potentials
• L6.4 – Electrochemical Series and Cell Potential
– Electrochemical Series
– Galvanic Series
– Reference Electrodes
– Cell Potential: Daniel Cell

Reference Book: W. D. Callister and D. G. Rethwisch, Materials Science and Engineering: An Introduction, John Willey & Sons ISBN: 9781119321590

Complementary Reference Book: P. A. Schweitzer, Fundamentals Of Corrosion: Mechanisms, Causes, and Preventative Methods, CRC Press ISBN:
9781420067705
 Lecture Structure
• L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
– Thermodynamics of Corrosion
– Chemical and Free Energy
– Electrochemistry of Corrosion
– Predicting Corrosion: Standard EMF Series
– Introduction to Types of Corrosion and Mechanisms
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
o Learning Objectives

✓ Understand the fundamental aspects of corrosion from a

thermodynamic and chemical/free energy standpoint

✓ Brief introduction to the electrochemical aspects of

corrosion

✓ Prediction of corrosion through the standard EMF series

✓ Introduction to types and mechanisms of corrosion

5
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Thermodynamics of Corrosion
Thermodynamics is the driving force of corrosion:
– Corrosion is controlled by the release or transfer of energy
– Corrosion is a spontaneous process
– Occurs with a release of free energy
– Extracting metals form their ores consumes vast amounts of
energy
– Much of this energy is “stored” in the metal
• Corrosion releases this energy back to the environment
Nature minimises the energy content of metal by corrosion

University of Adelaide 6
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Chemical and Free Energy
Partly from energy stored in chemical bonds within the metal—
Internal Energy
– Only a proportion of the internal energy is available as Free Energy

A + B = C + D + ΔG
Reactants Products Energy

Transition state AB exists briefly as A

reacts with B before forming C and D
AB has higher energy state than
A and B or C and D

University of Adelaide 7
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Chemical and Free Energy
– Driving force for corrosion is free energy
– All interactions between elements and compounds are governed by
the free energy changes available to them

– Spontaneous reaction requires a net release of free energy

– Free energy expressed as G
• Net change is ΔG
– Convention
• Energy given out is shown by –
• Energy absorbed is shown by +
For a spontaneous reaction ΔG must be negative

University of Adelaide 8
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Chemical and Free Energy
– Lower energy –> more stable (less tendency towards
corrosion)

– Electrochemical potential can be related to the change in

energy via:
G = –n E F
where ΔG = Change in Gibbs free energy (in Joules⸱mol–1)
n = Valency (number of electrons involved)
F = Faraday constant (96,494 C⸱mol–1)
E = Electrochemical potential (V)

– For G to be negative (spontaneous—G < 0) the

electrochemical potential of the reaction must be positive
(spontaneous—E > 0)

University of Adelaide 9
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Chemical and Free Energy
For a spontaneous reaction, ΔG must be negative
– At ambient temperature:
• Compounds of metals have lower values of G than the uncombined
metals
– Most metals have an inherent tendency to corrode
• Why don’t they just corrode away at all times?

We just have to
supply the transition
energy
Free energy of
activation ΔG‡

University of Adelaide 10
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Chemical and Free Energy
Why does not gold corrode?

Any ideas?

University of Adelaide 11
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Electrochemistry of Corrosion
Mechanism of Corrosion
Metals corrode by loss of electrons (oxidation)
– For example: M+ M+
M+
M+
M+
Fe Fe2+ + 2e M+ M+
M M+ M+
M+ M+
Formation of ions M+
M+
results in a loss of metal M+ M+
M+

Solid metal Ions in solution

University of Adelaide 12
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Electrochemistry of Corrosion
Wet Corrosion Cell
Four components:
– Anode (+)
• Corrodes by loss of e-
M = Mz+ + ze- (oxidation)
» z = valency
– Cathode (-)
• Consumes e-
Mz+ + ze- = M (reduction)
» does not normally corrode
H+ + e- = H, 2H= H2
– Electrolyte solution
– Connections
Remove one component and
corrosion stops
University of Adelaide 13
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Electrochemistry of Corrosion
Why does a piece of iron (Fe) corrode in acid?

Cathode (2H+ + 2e- H2(g))

2e-
2H+

Fe2+
Anode (Fe Fe2+ + 2e-)

Metal (Fe)
Ionic conductor
University of Adelaide 14
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Predicting Corrosion: Standard EMF Series
reaction Eo [volts vs SHE] EMF
Au3+ +3e- → Au +1.498 Galvanic Series or
O2 + 4H++4e- → 2H20 +1.229 Electropotential Series or
Fe3+ + e- → Fe2+ +0.771 Electromotive Force Series
O2 + 2H2O + 4e- → 4OH- +0.401
Cu2+ + 2e- → Cu +0.337
2H+ + 2e- → H2 0.000 Fe
Cu
Ni2+ + 2e- → Ni -0.250
Fe2+ + 2e- → Fe -0.440
Cr3+ + 3e- → Cr -0.744
Zn2+ + 2e- → Zn -0.763
2H2O + 2e- → H2 + 2OH- -0.828
Al3+ + 3e- → Al -1.662
Mg2+ + 2e- → Mg -2.363
Which metal will corrode?
University of Adelaide 15
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Introduction to Types of Corrosion and Mechanisms
There are different types of corrosion, each of them with their
specific mechanisms:
(i) General corrosion
(ii) Galvanic corrosion
(iii) Localised corrosion
– Pitting (factors such as passivation, Cl, pH)
– Crevice
– Differential concentration or aeration
(iv) Selective attack and intergranular corrosion
(v) Stress corrosion cracking and hydrogen embrittlement
(vi) Induced currents

University of Adelaide 16
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Introduction to Types of Corrosion and Mechanisms
(i) General (Uniform) Corrosion

University of Adelaide 17
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Introduction to Types of Corrosion and Mechanisms
(ii) Galvanic Corrosion: Dissimilar metals in contact

University of Adelaide 18
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Introduction to Types of Corrosion and Mechanisms
(iii) Localised Corrosion:
– Differential concentration
– Differential aeration
– Crevice corrosion
– Pitting

University of Adelaide 19
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Introduction to Types of Corrosion and Mechanisms
(iv) Selective and Intergranular Corrosion:

Selective Corrosion

Intergranular Attack

University of Adelaide 20
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Introduction to Types of Corrosion and Mechanisms
(v) Stress Corrosion:
Physical effects
– Fatigue
– Fretting
Cyclic tensile stress
– Cavitation
– Erosion
– Impingement (not shown)

University of Adelaide 21
L6.2 – Introduction to Thermodynamics and
Electrochemistry of Corrosion
• Introduction to Types of Corrosion and Mechanisms
(v) Stress Corrosion: Hydrogen Embrittlement
Stress Corrosion Cracking

University of Adelaide 22